Insecticidal Fertilizer Mixtures

ABSTRACT

This invention relates to insecticidal fertilizer mixtures containing 
     (a) an agonist or antagonist of ion channels in the insect nervous system;
 
(b) a fertilizer;
 
(c) optionally, an adherent; and
 
(d) optionally, one or more auxiliaries and/or carrier materials.

This application is a Continuation of U.S. application Ser. No.11/301,370, filed Dec. 13, 2005, the entire contents of which are herebyincorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

This invention relates to stable and efficacious insecticidal fertilizermixtures comprising a fertilizing component and an agonist or antagonistof ion channels in the insect nervous system.

Agonists and antagonists of ion channels in the insect nervous systemare known. It is also known to use fertilizer in granular form forbroadcast application to turfgrass and to use fertilizers for ornamentalhouseplants in the form of small fertilizer sticks or impregnatedcardboard strips that are pressed into nutrient substrate of the plants.Also known are mixtures of fertilizers granules with insecticides and/orother pesticide products for treatment of turfgrass and tabletscontaining dimethoate as insecticidal active substance and fertilizerfor treatment of ornamental houseplants, but the action of such mixturesis not completely satisfactory. For example, U.S. Pat. No. 5,783,203describes mixtures containing fertilizers and agonists or antagonist ofnicotinergic acetylcholine receptors of insects, but the methoddescribed therein, while useful in part because it can provide increaseduptake of peticidally active components into plants, has not been founduseful for preparing granular fertilizer mixtures that effectively andrapidly release ion channel agonist or antagonist into the soil. Liquidfertilizer systems, such as those containing agonist or antagonists ofnicotinergic acetylcholine receptors described in U.S. patentapplication Ser. No. 11/041,167, are also known but are not useful forsolid fertilizer systems.

SUMMARY OF THE INVENTION

This invention relates to insecticidal fertilizer mixtures comprising

a) an agonist or antagonist of ion channels in the insect nervoussystem;b) a fertilizer;c) optionally, an adherent; andd) optionally, one or more auxiliaries and/or carrier materials.

This invention further relates to dimensionally stable mixtures ofagonists or antagonists of ion channels in the insect nervous systemwith fertilizers, optional adherents, and optional auxiliaries andcarrier materials in the form of small sticks, plates, tablets orgranules, which increase the speed of action of the agonist orantagonist.

DETAILED DESCRIPTION OF THE INVENTION

The action of the mixtures according to the invention begins morerapidly than customary fertilizer-free granules containing the sameactive ingredient. The mixtures according to the invention can beemployed simply and without problems, specifically in non-commercialhorticulture.

Active ingredients that are effective according to the invention includeagonists or antagonists of ion channels, such as GABA-gated orglutamate-gated chloride (Cl⁻) channels, in the insect nervous system.Examples of suitable ion channel agonists are arylpyrazoles of formula(I)

in whichX represents N or C—R⁶,R¹ is CN, methyl, or halogen,R² is S(O)_(n)R⁷, 4,5-dicyanoimidazol 2-yl, or haloalkyl,R³ represents hydrogen, halogen, NR⁸R⁹, S(O)_(m)R¹⁰, C(O)R¹⁰, C(O)O—R⁷,alkyl, haloalkyl, OR¹¹, or —N═CR¹²R¹³,R⁴ and R⁶, independently of one another, represent hydrogen, halogen,CN, or NO₂,R⁵ represents halogen, haloalkyl, haloalkoxy, S(O)_(q)CF₃, or SF₅,R⁷ is alkyl or haloalkyl,R⁸ and R⁹ independently represent hydrogen, alkyl, haloalkyl, C(O)alkyl,alkoxycarbonyl, or S(O)_(r)CF₃; or R⁸ and R⁹ together optionally form adivalent alkylene radical that is optionally interrupted by one or twodivalent heteroatoms, such as oxygen or sulphur,R₁₀ represents alkyl or haloalkyl,R₁₁ represents hydrogen, alkyl, or haloalkyl,R₁₂ represents hydrogen or alkyl,R₁₃ represents phenyl or heteroaryl that is unsubstituted or optionallysubstituted by one or more halogen atoms or a member selected from thegroup consisting of OH, —O-alkyl, —S-alkyl, cyano, and alkyl, andm, n, q, and r, independently of one another, represent 0, 1, or 2.

Alkyl groups preferably have 1 to 6 carbon atoms and include, forexample, methyl, ethyl, i-propyl, and sec.- or t.-butyl. Haloalkylgroups preferably have 1 to 4 (more preferably 1 or 2) carbon atoms andpreferably 1 to 5 (more preferably 1 to 3) halogen atoms, where thehalogen atoms are identical or different and are preferably fluorine,chlorine, or bromine (more preferably fluorine), and include, forexample, trifluoromethyl. Alkoxy groups preferably have 1 to 4 (morepreferably 1 or 2) carbon atoms and include, for example, methoxy,ethoxy, n- and i-propyloxy, and n-, i- and t-butyloxy

When R¹ is methyl, it is generally preferred that either (1) X is N, R³is NH₂, R⁴ is Cl, R⁵ is CF₃, and R⁷ is haloalkyl, or (2) X is C—Cl, R²is 4,5-dicyanoimidazol-2-yl, R³ is Cl, R⁴ is Cl, R⁵ is CF₃. However, amore preferred group of effective 1-arylpyrazoles of the invention isthat wherein X is C—R⁶; R¹ is CN; R³ is NH₂; R⁴ and R⁶, independently ofone another, represent halogen; R⁵ is haloalkyl; and R⁷ is haloalkyl. Amost preferred 1-arylpyrazole is5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinyl-3-cyanopyrazole.

The contents of active substance are preferably from about 0.0001% toabout 1%, preferably from about 0.001% to about 0.1%, and morepreferably from about 0.005% to about 0.015%.

Suitable fertilizer components include organic and inorganicnitrogen-containing compounds such as urea, urea-formaldehydecondensation products, amino acids, ammonium salts and nitrates, as wellas potassium salts (preferably chlorides, sulfates, or nitrates) andphosphoric acid and/or salts of phosphoric acids (preferably potassiumsalts or ammonium salts). The fertilizers may also contain salts ofmicronutrients (preferably manganese, magnesium, iron, boron, copper,zinc, molybdenum, and/or cobalt) and phytohormones (e.g., vitamin B1 orindole-3-acetic acid). Commercially available complete fertilizers arepreferably employed.

The principal fertilizer constituents, nitrogen, potassium, andphosphorus, can be varied within wide limits. It is conventional to usecontents of from 1 to 30% of nitrogen (preferably from 5 to 20%), from 1to 20% of potassium (preferably from 3 to 15%), and from 1 to 20% ofphosphorus (preferably from 3 to 10%). The contents of microelements areusually in the ppm range, preferably from 1 to 1000 ppm.

The adherent component serves to establish and/or maintain physicalcontact between the fertilizer component and the other components of theinsecticidal fertilizer mixtures of the invention. When the agonist orantagonist component is soluble in a liquid adherent, the agonist orantagonist component can be initially dissolved or suspended in theadherent and then applied to the fertilizer by any conventional method,such as spraying or simple mixing. When the agonist or antagonistcomponent is not soluble in a liquid adherent, all of the components canfirst be mixed together until essentially homogenous, after which theadherent is applied in a manner that does not lead to excessiveaggregation of solid particles (when the agonist or antagonist componentand the fertilizer are solids) or to separation of liquid from solidcomponents (when the agonist or antagonist component is liquid).Suitable adherents are typically retained on the resultant insecticidalfertilizer mixtures, but it is also possible to use adherents thatevaporate or are washed away as long as they serve to establish and/ormaintain physical contact between components (a) and (b). Suitableadherents include known organic adhesives, including tackifiers, such ascelluloses or substituted celluloses, natural and synthetic polymers inthe form of powders, granules, or latices, and inorganic adhesives suchas gypsum, silica, or cement. However, it is also possible to usecompounds that are not ordinarily considered adhesives as long as theysuitably maintain physical contact between the various components.Particularly preferred adherents of this type are citric acid esters,such as Citroflex® esters. It is also possible to use organic orinorganic liquids that dissolve or suspend the agonist or antagonistcomponent but do not persist in substantial quantities, such as water,alcohols, esters, ketones, ethers, aromatics, and other known liquids.When such adherents are used, the insecticidal fertilizer mixtures ofthe invention retain little if any of the adherent once the mixtures areprepared. Regardless of the type of adherent used, the adherent isgenerally present in the mixture in concentrations of from 1 to 30% byweight, preferably from 2 to 20% by weight.

Suitable solid carrier materials include, for example, natural groundminerals, such as kaolins, aluminas, talc, chalk, quartz, attapulgite,montmorillonite, and diatomaceous earth, or synthetic ground minerals,such as highly dispersed silicic acid, aluminum oxide, silicates, andcalcium phosphates and calcium hydrogen phosphates. Suitable solidcarrier materials for granules include, for example, crushed andfractionated natural minerals, such as calcite, marble, pumice,sepiolite, and dolomite, or synthetic granules of inorganic and organicground materials, as well as granules of organic material, such assawdust, coconut husks, corn cobs, and tobacco stalks. Coatedfertilizers can also be used.

Suitable auxiliaries for the preparation of the mixtures according tothe invention include disintegrants and surfactants. Disintegrants areused to promote the release of the active substance in the soil. Cornstarch, crosslinked polyvinylpyrrolidone, and specific celluloses can beused individually or in combination. Disintegrants are present inconcentrations of from 1 to 20% by weight, preferably from 3 to 10% byweight. Surfactants are used to improve the biological activity of theactive substance by solubilization. Surfactants are present at a contentbetween 1 to 10% by weight, preferably from 2 to 5% by weight. Nonionicsurfactants of the alkyl-aryl-ethoxylate type are appropriate.

Granular fertilizers are particularly preferred. However, the mixturesof active substance, fertilizers, adhesive, auxiliary, and inertsubstances can, if desired, be mixed intensively and compressed by anextruder into small sticks with a diameter of from 3 to 10 mm,preferably from 6 to 8 mm, and a length of from 1 to 10 cm, preferablyfrom 3 to 6 cm. Alternatively, the mixture can be brought into thedesired form of small sticks using a tableting press. It is alsopossible to produce small sticks or tablets that are free from activesubstance and then to coat these sticks or tablets with a solution ofthe active substance. This subsequent coating operation can also be usedwith advantage to apply active substance to fertilizer granules.

The fertilizer mixtures according to the invention are suitable for thecontrol of insects that are encountered in horticulture, agriculture,and forestry. The fertilizer mixtures are active against normallysensitive and resistant species and against all or individual stages ofdevelopment. The above-mentioned pests include the following:

From the order of the Siphonaptera, for example, Ctenocephalides felis,Ctenocephalides canis, Pulex irritans, Spilopsyllus cuniculi, Tungapenetrans, and Xenopsylla cheopis.From the order of the Acari, for example, Rhipicephalus sanguineus,Ixodes pacificus, Ixodes scapularis, Amblyomma americanum, Amblyommamaculatum, Dermatocentor andersoni, Dermatocentor variabilis,Haemaphysalis chordeilis, and Boophilus annulatus.From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porecellio scaber.From the order of the Diplopoda, for example, Blaniulus guttulatus.From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.From the order of the Thysanura, for example, Lepisma saccharina.From the order of the Collembola, for example, Onychiurus armatus.From the order of the Orthoptera, for example, Scapteriscus spp. such asScapteriscus abbreviatus, Scapteriscus acletus, Scapteriscus borellii,Scapteriscus didactylus, and Scapteriscus vicinus, Neocurtillahexadactyla, Blatta orientalis, Periplaneta americana, Leucophaeamaderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp.,Locusta migratoria migratorioides, Melanoplus differentialis andSchistocerca gregaria.From the order of the Dermaptera, for example, Forficula auricularia.From the order of the Isoptera, for example Reticulitermes spp.From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Spodoptera exigua,Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusiani, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilussurinamensis, Anthonomus pp., Sitophilus spp., Otiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusspp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbiumpsylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderusspp., Melolontha melolontha, Amphimallon solstitialis and Costelytrazealandica.From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tanaus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

Particularly worthy of mention is the action against ants (particularlyfire ants), mole crickets, fleas, ticks, and other yard pests.

The compositions according to the invention are employed in a dose suchthat from about 0.01 to 100 mg/m² of active substance, preferably from0.1 to 10 mg/m² of active substance and particularly preferably from 0.1to 5 mg/m² of active substance, are employed.

The following examples further illustrate details for the preparationand use of the compositions of this invention. The invention, which isset forth in the foregoing disclosure, is not to be limited either inspirit or scope by these examples. Those skilled in the art will readilyunderstand that known variations of the conditions and processes of thefollowing preparative procedures can be used to prepare thesecompositions. Unless otherwise noted, all temperatures are degreesCelsius and all percentages are percentages by weight.

EXAMPLES Preparation of Test Sample

The following ingredients were used in the following proportions toprepare an insecticidal fertilizer mixture according to the invention:

Percent by weight Ingredient (based on total) Fipronil (90%) 0.008Citroflex A-4 1 Fertilizer 98.992The fertilizers used in the examples were 15-2-15, 0-0-7, and 24-8-15fertilizers.

Granular formulations were prepared by dissolving technical gradefipronil in the Citroflex A-4 and then spraying the resultant mixtureonto the fertilizer. Mixtures having a content of 72 ppm fipronil wereused in the tests described in the following Examples.

Stability

Long-term stability of a mixture prepared in this manner was determinedby comparing analyses of a blend of three samples conducted immediatelyafter preparation and three years after preparation. The initial contentof fipronil was found to be 0.0073%, whereas the content after threeyears was found to be 0.0066%.

In contrast, a mixture 0.42% fipronil (as Regent 300 EC, from

BASF) and 99.58% of 46-0-0 fertilizer initially contained 1048 ppmfipronil but after only one week at room temperature contained 930 ppmfipronil and after one week at 54° C. contained only 660 ppm fipronil.

Example 1

Plots of ca. 5000 ft² (ca. 465 m²) and containing an average of ninefire ant mounds per plot were laid out and treated in late fall. Numbersof live mounds in each plot were counted prior to treatment. Threereplicates of each treatment were tested. Granular formulations offipronil and 15-2-15 fertilizer according to the invention were comparedwith granular formulations of fipronil on a Biodac® cellulose-basedgranular carrier. Efficacy was assessed at 30, 60, and 90 days aftertreatment (“DAT”) (through mid-winter) by counting live mounds andcalculating the percent reduction in mounds relative to the pretreatmentcounts. Results are presented in Table 1.

TABLE 1 In-field efficacy of granular fipronil formulations against redimported fire ant, Solenopsis invicta Active % reduction in % ingredientfire ant mounds active Product applied 30 60 90 Treatment ingred.applied rate DAT DAT DAT Control  0%  3% 12% Fipronil on 143 ppm  87lbs/A 0.0125 lb/A 13% 24% 38% Biodac (10 g/m²) (1.4 mg/m²) Fipronil on 72 ppm 158 lbs/A 0.0125 lb/A 30% 42% 41% fertilizer (18 g/m²) (1.4mg/m²)

The data in Table 1 show that fipronil on fertilizer formulation killedmore ant mounds at 30 and 60 days after treatment than did the fipronilon Biodac granular carrier formulation.

Example 2

Plots size varied but each plot contained at least ten fire ant moundsper plot. The plots were treated in early summer. Numbers of live moundsin each plot were counted prior to treatment. Three replicates of eachtreatment were tested. Granular formulations of fipronil and 12-2-15fertilizer according to the invention were compared with granularformulations of fipronil on a Biodac® cellulose-based granular carrier.Efficacy was assessed at 12, 29, and 104 DAT (through early fall) bycounting live mounds and calculating the percent reduction in moundsrelative to the pretreatment counts. Results are presented in Table 2.

TABLE 2 In-field efficacy of granular fipronil formulations against redimported fire ant, Solenopsis invicta Active % reduction in % ingredientfire ant mounds active Product applied 12 29 104 Treatment ingred.applied rate DAT DAT DAT Control −6% 24% −12% Fipronil on 143 ppm  87lbs/A 0.0125 lb/A 20% 80%  90% Biodac (10 g/m²) (1.4 mg/m²) Fipronil on 72 ppm 158 lbs/A 0.0125 lb/A 49% 94%  96% fertilizer (18 g/m²) (1.4mg/m²)

The data in Table 2 show that fipronil on fertilizer formulation killedmore ant mounds at 12 and 29 days after treatment than did the fipronilon Biodac granular carrier formulation

Example 3

Plots of ca. 5000 ft² (ca. 465 m²) and containing an average oftwenty-one fire ant mounds per plot were laid out and treated in latefall. Numbers of live mounds in each plot were counted prior totreatment. Four replicates of each treatment were tested. Granularformulations of fipronil and 0-0-7 fertilizer according to the inventionwere compared with granular formulations of fipronil on a Biodac®cellulose-based granular carrier. Efficacy was assessed at 1, 3, and 4weeks after treatment (“WAT”) by counting live mounds. Results arepresented in Table 3.

TABLE 3 In-field efficacy of granular fipronil formulations against redimported fire ant, Solenopsis invicta % Active fire ant mounds per plotactive Product ingredient 0 1 3 4 Treatment ingred. applied applied rateDAT WAT WAT WAT Control 22.0 34.8 27.3 35.8 Fipronil on 143 ppm  87lbs/A 0.0125 lb/A 21.8 22.3 1.3 6.5 Biodac (10 g/m²) (1.4 mg/m²)Fipronil on  72 ppm 158 lbs/A 0.0125 lb/A 21.3 16 2.5 5 fertilizer (18g/m²) (1.4 mg/m²)

The data in Table 3 show that fipronil on fertilizer formulation killedmore ant mounds at 1 week after treatment than did the fipronil onBiodac granular carrier formulation. At 3 weeks after treatment theefficacy of the two formulations was identical.

Example 4

Plots of ca. 5000 ft² (ca. 465 m²) and containing an average of 44 fireant mounds per plot were laid out and treated in spring. Numbers of livemounds in each plot were counted prior to treatment. Four replicates ofeach treatment were tested. Granular formulations of fipronil and24-8-15 fertilizer according to the invention were compared withgranular formulations of fipronil on a Biodac® cellulose-based granularcarrier. Efficacy was assessed at 3, 7, and 14 days after treatment(“DAT”) and at 1 and 2 months after treatment (“MAT”) by counting livemounds. Results are presented in Table 4.

TABLE 4 In-field efficacy of granular fipronil formulations against redimported fire ant, Solenopsis invicta % Active fire ant mounds per plotactive Product ingredient 0 3 7 14 1 2 Treatment ingred. applied appliedrate DAT DAT DAT DAT MAT MAT Control 43 43 47 58 74 46 Fipronil on 143ppm  87 lbs/A 0.0125 lb/A 47 42 38 12 8 1 Biodac (10 g/m²) (1.4 mg/m²)Fipronil on  72 ppm 158 lbs/A 0.0125 lb/A 40 36 25 0 0 0 fertilizer (18g/m²) (1.4 mg/m²)

The data in Table 4 show that fipronil on fertilizer formulation killedmore ant mounds at 3 and 7 days after treatment than did the fipronil onBiodac granular carrier formulation. By 14 days after treatment,fipronil on fertilizer had eradicated the fire ant mounds in the treatedplots. An equivalent level of control was not observed in the fipronilon Biodac plots until two months after treatment.

1. An insecticidal fertilizer mixture comprising (a) an agonist orantagonist of ion channels in the insect nervous system; (b) afertilizer; (c) optionally, an adherent; and (d) optionally, one or moreauxiliaries and/or carrier materials.
 2. The mixture according to claim1 wherein component (a) is an arylpyrazole of formula (I)

in which X represents N or C—R⁶, R¹ is CN, methyl, or halogen, R² isS(O)_(n)R⁷, 4,5-dicyanoimidazol 2-yl, or haloalkyl, R³ representshydrogen, halogen, NR⁸R⁹, S(O)_(m)R¹⁰, C(O)R¹⁰, C(O)O—R⁷, alkyl,haloalkyl, OR¹¹, or —N═CR¹²R¹³, R⁴ and R⁶, independently of one another,represent hydrogen, halogen, CN, or NO₂, R⁵ represents halogen,haloalkyl, haloalkoxy, S(O)_(q)CF₃, or SF₅, R⁷ is alkyl or haloalkyl, R⁸and R⁹ independently represent hydrogen, alkyl, haloalkyl, C(O)alkyl,alkoxycarbonyl, or S(O)_(r)CF₃; or R⁸ and R⁹ together optionally form adivalent alkylene radical that is optionally interrupted by one or twodivalent heteroatoms, R₁₀ represents alkyl or haloalkyl, R₁₁ representshydrogen, alkyl, or haloalkyl, R₁₂ represents hydrogen or alkyl, R₁₃represents phenyl or heteroaryl that is unsubstituted or optionallysubstituted by one or more halogen atoms or a member selected from thegroup consisting of OH, —O-alkyl, —S-alkyl, cyano, and alkyl, and m, n,q, and r, independently of one another, represent 0, 1, or
 2. 3. Themixture according to claim 2 in which X is C—R⁶, R¹ is CN, R² isS(O)_(n)R⁷, R³ is NH₂, R⁴ and R⁶, independently of one another,represent halogen, R⁵ is haloalkyl, and R⁷ is haloalkyl.
 4. The mixtureaccording to claim 1 wherein component (a) is5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinyl-3-cyanopyrazole.5. A process for preparing an insecticidal fertilizer mixture accordingto claim 1 comprising (a) dissolving or suspending an agonist orantagonist of ion channels in the insect nervous system in an adherent,and (b) applying the solution or suspension from step (a) to thefertilizer and optional auxiliaries and/or carriers.
 6. A process forpreparing an insecticidal fertilizer mixture according to claim 1comprising (a) mixing an agonist or antagonist of ion channels in theinsect nervous system with a fertilizer and an adherent and optionallyone or more auxiliaries and/or carriers, and (b) compressing orextruding the resultant mixture into a desired form.
 7. The mixtureaccording to claim 1 comprising (a) an agonist or antagonist of ionchannels in the insect nervous system; (b) a fertilizer; (c) an adherentin which component (a) is soluble; and (d) optionally, one or moreauxiliaries and/or carrier materials.
 8. The mixture according to claim7 wherein the adherent is a citric acid ester.
 9. A method of protectingplants from unwanted insects comprising adding an insecticidallyeffective amount of a mixture according to claim 1 into a nutrientmedium of such plants.
 10. An insecticidal fertilizer mixture accordingto claim 1 comprising (a) an arylpyrazole of formula (I)

in which X represents N or C—R⁶, R′ is CN, methyl, or halogen, R² isS(O)_(n)R⁷, 4,5-dicyanoimidazol 2-yl, or haloalkyl, R³ representshydrogen, halogen, NR⁸R⁹, S(O)_(m)R¹⁰, C(O)R¹⁰, C(O)O—R⁷, alkyl,haloalkyl, OR¹¹, or —N═CR¹²R¹³, R⁴ and R⁶, independently of one another,represent hydrogen, halogen, CN, or NO₂, R⁵ represents halogen,haloalkyl, haloalkoxy, S(O)_(q),CF₃, or SF₅, R⁷ is alkyl or haloalkyl,R⁸ and R⁹ independently represent hydrogen, alkyl, haloalkyl, C(O)alkyl,alkoxycarbonyl, or S(O)_(r)CF₃; or R⁸ and R⁹ together optionally form adivalent alkylene radical that is optionally interrupted by one or twodivalent heteroatoms, R₁₀ represents alkyl or haloalkyl, R₁₁ representshydrogen, alkyl, or haloalkyl, R₁₂ represents hydrogen or alkyl, R₁₃represents phenyl or heteroaryl that is unsubstituted or optionallysubstituted by one or more halogen atoms or a member selected from thegroup consisting of OH, —O-alkyl, —S-alkyl, cyano, and alkyl, and m, n,q, and r, independently of one another, represent 0, 1, or 2, (b) afertilizer; (c) optionally, an adherent; and (d) optionally, one or moreauxiliaries and/or carrier materials, wherein the insecticidalfertilizer mixture is in the form of a stick, plate, tablet, or granule.11. A process for the preparation of an insecticidal fertilizer mixtureaccording to claim 10 comprising (a) mixing an arylpyrazole of formula(I) with a fertilizer and an adherent and optionally one or moreauxiliaries and/or carriers, and (b) compressing or extruding theresultant mixture into a desired form.
 12. A method of protecting plantsfrom unwanted insects comprising adding an insecticidally effectiveamount of a mixture according to claim 9 into a nutrient medium of suchplants.